Vacuum brazing of TZM alloy and ZrCp-W composite was achieved by using Ti-50Ni (at. %) eutectic brazing alloy. The typical interfacial microstructure of brazed joints was TZM/Ti-Mo+TiNi3+Mo-Ti-W/TiNi+TiNi3+W(s,s)+TiC/ZrCp-W, which was characterized using SEM, EDS and XRD. In addition, the effect of brazing temperature on interfacial microstructure and joining properties of TZM/Ti-50Ni/ZrCp-W brazed joints was investigated in detail. As the brazing temperature increased, more and more elements Ti and Ni in molten brazing alloy diffused into the base materials, which in turn broaden the brazed joints. At the same time, the grain size gradually increased and the grain boundary became smoother. Experimental results demonstrated that reliable brazed joints with average shear strength up to 146 MPa was achieved when brazed at 1340 °C for 10 min.